22-Sep-21 News Discovery of 1,1-Bis(diphenylphosphino)ferrocene

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N,N-Diethyl-N?-4-nitrobenzoylselenourea (HLSe) reacts with the mono- and dinuclear phosphine gold(I) chloro complexes [AuCl(PR 3)] (R=Ph, o-tol, Et) and [Au2Cl2(mu-P-P)] (P-P=dppm, dppe, dppp, dppb, dppf) in the presence of base to give gold(I) phosphine selenoureato complexes [Au(LSe)(PR3)] [R=Ph (1), o-tol (2), Et (3)], [Au2(LSe)2(mu-P-P)] [P-P=dppm (4), dppe (5), dppp (6), dppb (7), dppf (8)] in excellent yields. The compounds were fully characterised by spectroscopic methods and, in the case of compounds 1, 5 and 8, by single crystal X-ray diffraction. The compounds consist of a gold atom bound in linear fashion to the phosphine ligand and the selenium atom from the deprotonated acylselenourea. These complexes thus represent the first examples of acylselenoureato metal compounds in which the ligands do not adopt the typical O,Se chelating mode but rather coordinate to the metal only through the selenium atom.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

9/22/21 News Awesome and Easy Science Experiments about (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine)

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A highly reactive electrophilic bromodifluoromethylthiolating reagent, alpha-cumyl bromodifluoro-methanesulfenate 1, was prepared to allow for direct bromodifluoromethylthiolation of aryl boron reagents. This coupling reaction takes place under copper catalysis, and affords a large range of bromodifluoromethylthiolated arenes. These compounds are amenable to various transformations including halogen exchange with [18F]KF/K222, a process giving access to [18F]arylSCF3 in two steps from the corresponding aryl boronic pinacol esters.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

22-Sep-21 News More research is needed about (Oxybis(2,1-phenylene))bis(diphenylphosphine)

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166330-10-5, Name is (Oxybis(2,1-phenylene))bis(diphenylphosphine), molecular formula is C36H28OP2, belongs to chiral-phosphine-ligands compound, is a common compound. In a patnet, once mentioned the new application about 166330-10-5, Recommanded Product: 166330-10-5

A novel Pt tetradentate complexs having Pt-O bond is disclosed. These complexes are useful as emitters in phosphorescent OLEDs.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

09/18/21 News Can You Really Do Chemisty Experiments About 1,1-Bis(diphenylphosphino)ferrocene

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Previous reports in the literature have established the utility of 1,1?-bis(diphenylphosphino)ferrocene (DPPF, LPh) in the nickel-catalyzed cross-coupling of (hetero)aryl electrophiles with primary or secondary amines. In an effort to evaluate the effect of varying the PR2-donor groups on catalytic performance in such transformations, a series of 10 structurally varied 1,1?-bis(bis(alkyl/aryl)phosphino)ferrocene ancillary ligands (LX) were systematically examined in selected competitive test cross-couplings of (hetero)aryl halides with furfurylamine, morpholine, and indole employing Ni(COD)2/LX catalyst mixtures. In addition to the excellent performance observed for the parent ligand LPh in a number of the test transformations explored, selected dialkylphosphino (e.g., DiPPF, LiPr) and meta-disubstituted diarylphosphino variants of LPh also proved highly effective. In particular, the electron-deficient ligand variant LCF3 featuring 3,5-bis(trifluoromethyl)phenyl groups on phosphorus was found to exhibit superior catalytic performance relative to LPh in most of the test transformations involving the N-arylation of indole. Our efforts to prepare Ni(II) precatalysts of the type (LX)Ni(o-tolyl)Cl, in analogy with known (LPh)Ni(o-tolyl)Cl, by employing several literature methods met with mixed results. Whereas (LiPr)Ni(o-tolyl)Cl was prepared straightforwardly and was crystallographically characterized, the use of LCF3 or ligands featuring tert-butyl (LtBu), o-tolyl (Lo-tol), or 4-methoxy-3,5-dimethylphenyl (LOMe) groups on phosphorus under similar conditions resulted in poor conversion to product and/or the formation of poorly soluble materials, highlighting the limitations of this commonly used precatalyst design.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

09/18/21 News Some scientific research about (Oxybis(2,1-phenylene))bis(diphenylphosphine)

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A series of [ReBr2(MeCN)(NO)(P?P)] complexes (P?P = 1,10-bis(diphenylphosphino)ferrocene (dppfc) (1a), 1,10- bis(diisopropylphosphino)ferrocene (diprpfc) (1b), 2,20-bis(diphenylphosphino) diphenyl ether (dpephos) (1c), 10,11-dihydro-4,5-bis(diphenylphosphino) dibenzo[b,f]oxepine (homoxantphos) (1d), 4,6-bis(diphenylphosphino)-10,10- dimethylphenoxasilin (Sixantphos) (1e)) were prepared with diphosphines varying in the P-Re-P bite angles. 1a,c-e were obtained from the reaction of [ReBr 5(NO)][NEt4]2 with an excess of the respective diphosphine in MeCN or MeCN/THF mixtures at elevated temperatures. Compound 1b was obtained by an alternative route, cleaving the dinuclear [{ReBr(mu2- Br)(NO)(diprpfc)}2] unit (2b) with MeCN. 2b was prepared from the reaction of [ReBr5(NO)][NEt4]2 with diprpfc in EtOH. The reaction of 1a-d with HSiEt2 gave the seven-coordinate [ReBr(H)2(SiEt3)(NO)(PnP)] compounds 4a-d, of which 4a,c,d are only stable in solution in the presence of HSiEt3. The SiMe3 (4f) and SiCl3 (4g) derivatives of 4b were also prepared by applying the reaction of 1b with HSiMe3 and HSiCl3. 1a,c,e, 2b, and 4f,g were structurally characterized. For 1c,e, 2b, and 4f,g NO/Br disorder was observed, which originates from the presence of two isomeric forms in the crystals of the respective compounds. For 1c,d fast interconversion of these isomers could be observed in their 31P{1H} NMR spectra at room temperature.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

Sep-21 News Awesome and Easy Science Experiments about 1,1-Bis(diphenylphosphino)ferrocene

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Thermal decomposition of the palladium (aryl)neopentoxide complexes [P-P]Pd(Ar)OCH2CMe3 [P-P =Tol-BINAP or BINAP; Ar p-C6H4CHO (1b), p-C6H4COPh (1c), p-C6H4NO2 (1d), o-C6H4NO2 (1e), o-C6H4CN (1F)] possessing substituents on the palladium-bound aryl group suitable for delocalization of negative charge led to quantitative (?95%) formation of aryl ether without detectable beta-hydride elimination. Thermal decomposition of 1b-f obeyed first-order kinetics, and the rate of reductive elimination decreased in the order o-NO2 > p-NO2 > p-CHO > p-COPh > o-CN. Conversely, thermal decomposition of the related derivatives [P-P]Pd(Ar)OCH2CMe3 [P-P = Tol-BINAP or BINAP; Ar p-C6H4Cl (1g), m-C6H4NO2 (1h), m-C6H4CN (1i)] which did not possess a resonance stabilizing group on the palladium-bound aryl group led to no detectable formation of aryl ether. These and related data point to the buildup of negative charge in the palladium-bound aryl group in the transition state for C-O reductive elimination and are consistent with a mechanism initiated by inner-sphere nucleophilic attack of the alkoxide ligand at the ipso-carbon atom of the palladium-bound aryl group through a zwitterionic Meisenheimer-type intermediate or transition state.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

09/17/21 News Awesome and Easy Science Experiments about (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine)

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Rhodium/iodide catalysts modified with the xantphos ligand are active for the homogeneous carbonylation of methanol to acetic acid using either pure CO or CO/H2. Residues from catalytic reactions contain a Rh(III) acetyl complex, [Rh(xantphos)(COMe)I2] (1), which was isolated and crystallographically characterized. The xantphos ligand in 1 adopts a “pincer” kappa3-P,O,P coordination mode with the xanthene oxygen donor trans to the acetyl ligand. The same product was also synthesized under mild conditions from [Rh(CO)2I]2. Iodide abstraction from 1 in the presence of donor ligands (L = MeCN, CO) gives the cationic acetyl species [Rh(xantphos)(COMe)I(L)]+, whereas in CH 2Cl2 migratory CO deinsertion gives [Rh(xantphos)(Me)I(CO) ]+ (4), which reacts with H2 to liberate methane, as observed in catalytic reactions using syngas. A number of Rh(I) xantphos complexes have been synthesized and characterized. Oxidative addition of methyl iodide to the cation [Rh(xantphos)(CO)]+ is very slow but can be catalyzed by addition of an iodide salt, via a mechanism involving neutral [Rh(xantphos)(CO)I] (6). IR spectroscopic data and DFT calculations for 6 suggest the existence in solution of conformers with different Rh-O distances. Kinetic data and activation parameters are reported for the reaction of 6 with MeI, which proceeds by methylation of the Rh center and subsequent migratory insertion to give 1. The enhancement of nucleophilicity arising from a Rh- – -O interaction is supported by DFT calculations for the SN2 transition state. A mechanism for catalytic methanol carbonylation based on the observed stoichiometric reaction steps is proposed. A survey of ligand conformations in xantphos complexes reveals a correlation between P-M-P bite angle and M-O distance and division into two broad categories with bite angle <120 (cis) or >143 (trans).

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

17-Sep News Archives for Chemistry Experiments of (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine)

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The trifluoromethyl and perfluoroalkyl functional groups possess significant thermal, chemical, and metabolic stability, as well as high lipophilicity and electronegativity. These physicochemical properties render fluorinated carbon residues indispensable in diverse applications, such as agrochemistry, drug design, and material chemistry. The generation and properties of nucleophilic perfluoroalkyl reagents as well as the scope and limitations of their additions to various electrophilic partners is described in this chapter.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

17-Sep News More research is needed about (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine)

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A compound of formula (I) wherein R1 is hydrogen or fluoro; R2 and R3 are independently selected from hydrogen or methyl, or a pharmaceutically acceptable salt thereof; pharmaceutical formulations containing said compound; the use of said compound in therapy; the use for the treatment of conditions associated with glycogen synthase kinase-3 related disorders, such as Alzheimer”s disease, as well as methods of treatment of said disorders, comprising administering to subjects in need of such treatment, a therapeutically effective amount of said compound.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate

9/17/21 News The Absolute Best Science Experiment for (9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine)

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Children learn through play, and they learn more than adults might expect. Science experiments are a great way to spark their curiosity, get their minds active, and encourage them to do something that doesn’t involve a screen. 161265-03-8, C39H32OP2. A document type is Article, introducing its new discovery., Product Details of 161265-03-8

A common strategy to synthesize 4/6-(4-(4-methylpiperazin-1-yl)-6-(4-(4- oxo-2-phenylthiazolidin-3-yl)phenyl)-1,3,5-triazin-2-yloxy)benzonitriles/ nicotinonitriles was developed by applying an efficient palladium-catalyzed C-C Suzuki coupling. Moreover, the synthesized compounds were also tested for their in vitro antimycobacterial activity against Mycobacterium tuberculosis H 37Rv using BACTEC MGIT and Lowenstein-Jensen MIC methods. Several compounds displayed profound antimycobacterial activity in combination with low toxicity towards mammalian cells. The best results were observed amongst the nicotinonitrile substituted s-triazine analogs and it could be a potential starting point to develop new lead compounds in the fight against M. tuberculosis H37Rv. The newly synthesized compounds were characterized by IR, 1H NMR, 13C NMR, MS and elemental analysis.

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Reference:
Phosphine ligand,
Chiral phosphine ligands in asymmetric synthesis. Molecular structure and absolute configuration of (1,5-cyclooctadiene)-(2S,3S)-2,3-bis(diphenylphosphino)butanerhodium(I) perchlorate tetrahydrofuran solvate